EP0548130B1 - Verfahren zur herstellung von russ und also hergestelltes russ - Google Patents

Verfahren zur herstellung von russ und also hergestelltes russ Download PDF

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Publication number
EP0548130B1
EP0548130B1 EP91915755A EP91915755A EP0548130B1 EP 0548130 B1 EP0548130 B1 EP 0548130B1 EP 91915755 A EP91915755 A EP 91915755A EP 91915755 A EP91915755 A EP 91915755A EP 0548130 B1 EP0548130 B1 EP 0548130B1
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EP
European Patent Office
Prior art keywords
carbon black
phase
pyrolysis
degrees celsius
temperature
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP91915755A
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English (en)
French (fr)
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EP0548130A1 (de
Inventor
Wilhelmus Johannes Henricus Schippers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
VAN DER HEIJDEN Iris de Pace Maria Paloma
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VAN DER HEIJDEN Iris de Pace Maria Paloma
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion

Definitions

  • the invention relates to a method for manufacturing carbon black.
  • Carbon black is often used as a filler or a reinforcement agent which is added to polymers, especially to rubber and elastomers. Carbon black is also suitable as a pigment for printing ink, coatings etc.
  • Prior art methods for manufacturing carbon black start from hydrocarbons which are cracked and/or incompletely calcinated at high temperatures. Such methods are for instance described in the Dutch patent applications No. 8004048 and 8801112. As is started from hydrocarbons, at the used temperatures which may exceed 1000 degrees Celsius, products which are hazardous to the environment may possibly be created, such as PCB's and nitrosaminebearers. These products are thus found in the obtained carbon black. These products are mainly formed when starting from chlorinated hydrocarbons.
  • the present invention aims at a new method to manufacture carbon black whereby, in an economical and environmentally favourable way, a new kind of carbon black is obtained, presenting excellent and environmentally favourable characteristics, which is especially suitable as an additif to elastomers, printing ink and coatings and whereby the presence in the carbon black of hazardous products can easily be avoided.
  • vegetal material and/or animal waste material and/or algae is or are first compacted to the desired density and dry substance content and then subjected to a biochemical pre-processing comprising an irradiation by electromagnetic radiation, during which care is taken that the temperature of the material remains under 70 degrees Celsius, so that a strongly increased activity of thermophilic bacteria and an acceleration of the gel formation of the binding protein plasm between the cells occurs and a break-up of the organic cells takes place, after which the obtained material is subjected to a pyrolysis comprising three phases: a first phase wherein principally moisture, inclusive bound moisture is released, a second phase at higher temperatures wherein principally evaporatable hydrocarbons are released by evaporation and a third phase, at still higher temperatures, wherein the carbonizing of the remaining cell nuclei to carbon black is performed.
  • a biochemical pre-processing comprising an irradiation by electromagnetic radiation, during which care is taken that the temperature of the material remains under 70 degrees Celsius, so that a strongly increased activity of thermophil
  • a pyrolysis is performed without oxidation agents.
  • Such oxidation agents are for instance, air, which means that the pyrolysis is performed in an anaerobic way.
  • the material is irradiated with magnetic wave pulses having a frequency between 800 and 1100 MHz.
  • the invention also relates to the carbon black manufactured according to the method according to one of the above-mentioned embodiments.
  • carbon black having excellent characteristics one starts from organic material in a relative solid form, having a dry dust content higher than 50%. Possibly a quantity of mineral material may be added to this organic material, but the quantity of mineral material has to be smaller than the quantity of organic material.
  • organic material are especially suitable animal waste products such as chicken manure and/or vegetable material and algae, preferably so-called "blue green algae (cyanophytes)".
  • blue green algae cyanophytes
  • the quality and the characteristic of the obtained carbon black will be influenced by the composition of the starting material.
  • This starting material is consequently subjected to a biochemical pre-processing and a pyrolysis.
  • the biochemical pre-processing comprises a compacting in a hydraulic press 1 and an irradiation with electromagnetic waves in a magnetron 2.
  • the compressing can be effected in several steps and by using smaller pistons which are mounted in the main piston and which can penetrate the mass compacted by the main piston, a homogenization of the material may be obtained.
  • the compacting is performed using a pressure higher than 24,500 kPa and preferably higher than 27,440 kPa, but not higher than 29,400 kPa.
  • a homogeneous mass is obtained, having a density equal to or higher than 280 kg per square centimeter power of resistance, and whereof the temperature is raised to 30-35 degrees Celsius and the moisture content decreased.
  • the compacted homogeneous material is then irradiated in the magnetron 2 during at least 20 minutes and preferably about 30 minutes with electromagnetic pulses of, for instance 5 s with a frequency between 800 and 1100 MHz, and preferebly between 900 and 920 MHz.
  • electromagnetic pulses of, for instance 5 s with a frequency between 800 and 1100 MHz, and preferebly between 900 and 920 MHz.
  • a magnetron having a power between 5 and 12 kW and preferably between 6,8 to 7,6 kW is used. Care is taken that the irradiation waves are evenly distributed upon the material. Therefore wave conductors may be used. Consequently the material is irradiated on top, underneath and on each side. The irradiation is performed in a poor air environment, and thus in an almost completely anaerobic way.
  • the object of the irradiation is to activate specific anaerobic thermophilic bacteria such as for instance stearo-type bacteria which naturally present already a Brown movement.
  • the frequency is thus selected that not so much friction between the molecules appears and consequently heating, as the activation of the Brown movement of bacteria and cell organisms. Therefore extreme care has to be taken to prevent the temperature of the material, because of friction between the molecules, to rise higher than 70 degrees Celcius.
  • the temperature will also rise.
  • the temperature may not remain at about 30 to 40 degrees Celsius, whereas, due to the activity of Psychro and Mesophyle bacteria, methane gas could be formed.
  • the magnetron 2 is a closed tunnel.
  • the material is moved through this tunnel by means of a conveyor belt, preferebly made from Teflon (registered trademark) or Keplar (registered trademark).
  • thermophilic bacteria By the processing in the magnetron a biological decomposition process of the organic material takes place and a strongly increased activity of thermophilic bacteria and an acceleration of the gel formation of the binding protein plasm occurs, which entails a break-up of the organic cells.
  • the material is decomposed by an increase of enzymes and plasma from the binding fibre structure and from the break-up of the cells and cell nuclei.
  • the irradiated and already partially decomposed material is crumbled in a device 3, whereupon the crumbled material is subjected, still without supplying oxidation agents and thus, among other things, without addition of air, and under an atmospheric pressure, in the reactor 4 to a pyrolysis comprising three phases. During the crumbling the released moisture is eliminated.
  • the incoming material having a temperature of about 70 degrees Celsius is heated to a temperature between 200 and 250 degrees Celsius whereby principally all the moisture, inclusive molecular bound moisture, is released.
  • the released moisture is conveyed out of the reactor zone 5 and condenses in the condensor 8.
  • the remaining material is heated in a second reactor zone 6 up to a temperature of approximately 480 degrees Celsius.
  • Hydrocarbons which evaporate in this second zone are among other things unsaturated hydrocarbons such as ethylene and acethylene, alkenes such as ethene, propene and butene, aromatic hydrocarbons such as benzene, toluene and xylene and certain saturated hydrocarbons such as kerosines, naftalenes, ethylene tars.
  • These released hydrocarbons are conveyed from the reactor zone 6 without their being in contact with the outflowing water and principally the gases which are released in the next reactor zone 7.
  • the conveyed hydrocarbons are condensed in a condensor 9.
  • the condensed hydrocarbons can possibly be used as fuel for the heating of the reactor zones.
  • the material is heated to a temperature of 520 to 580 degrees Celsius, preferably to 538 degrees Celsius and this material is kept at this temperature for 20 to 30 minutes and preferably 22 to 25 minutes.
  • this third phase a carbonization of the material occurs, these are the remaining cell nuclei, whereby carbon black is formed.
  • the flowing through of the material from one reactor zone to the other is effected by means of mixture control screws and gas locks (so-called "air locks").
  • the gasses released during the last mentioned phase and among other things during the carbonizing process, are conveyed through 10.
  • the obtained solid pulverised carbon black which is conveyed from the last reactor zone 7, still without supplying an oxidizing agent, is quenched or cooled. Possible unwanted by-products which might be present in the carbon black are separated.
  • the carbon black is possibly subjected to further post-processing such as sifting, grinding, degritting, ilutriating (separation) or the formation of grains or platelets or pellets.
  • a new kind of carbon black is obtained with excellent characteristics which contain no products which are hazardous to the environment such as PCB's and nitrosaminebearers.
  • This kind of carbon black presents the following characteristics:
  • the absorption surface of iodine of the carbon black is determined as follows: a carbon black sample is placed in a porcelain crucible, provided with a loose lid to enable the gasses to escape, and calcinated at a temperature of 927 degrees Celsius during 7 min. and afterwards cooled in an exsiccator. The top layer of the calcinated carbon black is removed to a depth of approximately 0,635 cm. A suitable sample is weighed from the remaining carbon black in the crucible. A sample of 0,1 g is suitable for carbon black with an expected surface of 380 m 2 /g. The sample is placed in a flask and fourty ml of 0,0473 N iodine solution is added.
  • the flask is closed en shaken during 10 minutes at a speed of 120-260 up and down movements per minute.
  • the obtained solution is immediately centrifugated at 1200-2000 rotations per minute until the solution becomes clear, this means mostly 1 to 3 minutes.
  • As blanco sample 40 ml of the 0,0473 N iodine solution is shaken, centrifugated and titrated as described above.
  • the carbon black manufactured according to the method described above has an iodine surface higher than 380 m 2 / g.
  • Palettized carbon black obtained according to the above method has a DBF value higher than 200 ml/100 g.
  • the pH of a 5 g solution of the obtained palettized carbon black in 50 ml distilled water, boiled for 10 minutes, is measured.
  • the pH is less than 5.
  • the iodine addition number of the carbon black according to ISO 1304 is 380 g/kg.
  • the specific weight of the obtained carbon black after drying for 24 hours at 105 degrees Celsius in a pyrolitic oven is 0,8 g/cm 3 .
  • the specific surface measured with C0 2 adsorption at 273 K lies between 35 and 200 m 2 /g, and measured with N 2 at 77 K between 10 and 30 m 2 /g.
  • the diameter of the particles varies from 4 to 200 nanometer.
  • the carbon black has a wide range of particle sizes.
  • the d50 amounts to 51 micrometer.
  • the BET surface measured with N 2 adsorption at -196 degrees Celsius has a value of at least 34 m 2 /g.
  • the obtained carbon black is mixed with among other things ethylene-propylene-rubber (EPDM), after being dried in a pyrolitic oven at 105 degrees Celsius for 24 hours, in a proportion of 70 parts of carbon black per 100 parts of polymer, in a Banbury-mixing device GK2 of Werner & Pfleiderer.
  • EPDM ethylene-propylene-rubber
  • the same mixture is manufactured but whereby the carbon black obtained according to the invention is replaced by a commercial carbon black, namely Cancarb Thermax carbon black. Both carbon blacks show a normal mixing behaviour. After the mixing, the mixtures are conveyed through a two roller grinding device and formed into sheets for further testing.
  • the new carbon black obtained by the method described above is very satisfying for applications in rubbers and elastomers.
  • the physical characteristics are easily influenced by modifying the conditions of the method within the determined limits and by the choice of the starting material.
  • carbon blacks can be manufactured which can be classified according to the ASTM code from N110 to N990.
  • Preferably carbon blacks are manufactured with a classification comparable to "medium thermal".
  • the physical characteristics of the carbon black are comparable to these obtained with carbon black which is known on the market under the name THERMAX 991.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Carbon And Carbon Compounds (AREA)

Claims (13)

1. Verfahren zur Herstellung von Ruß, dadurch gekennzeichnet, daß pflanzliches Material und/oder tierisches Abfallmaterial und/oder Algen zunächst bis auf die gewünschte Dichte und Trockensubstanzgehalt verdichtet wird oder werden und dann einer biochemischen Vorbehandlung unterworfen werden, welche eine Bestrahlung durch elektromagnetische Strahlung umfaßt, während derer dafür gesorgt wird, daß die Temperatur des Materials unter 70 Grad Celsius bleibt, so daß eine stark erhöhte Aktivität thermophiler Bakterien und eine Beschleunigung der Gelbildung des verbindenden Proteinplasmas zwischen den Zellen auftritt und ein Aufbrechen der organischen Zellen stattfindet, wonach das erhaltene Material einer Pyrolyse unterworfen wird, welche drei Phasen umfaßt: eine erste Phase, worin hauptsächlich Feuchtigkeit, einschließlich gebundener Feuchtigkeit, freigesetzt wird, eine zweite Phase bei höheren Temperaturen, worin hauptsächlich verdunstbare Kohlenwasserstoffe durch Verdunstung freigesetzt werden, und eine dritte Phase, bei noch höheren Temperaturen, worin die Karbonisation der verbleibenden Zellnuklei zu Ruß durchgeführt wird.
2. Verfahren gemäß dem vorgenannten Anspruch, dadurch gekennzeichnet, daß die erste Phase der Pyrolyse bei einer Temperatur bis zu maximal 250 Grad Celsius durchgeführt wird.
3. Verfahren gemäß einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß die zweite Phase der Pyrolyse bei einer Temperatur zwischen 250 und 480 Grad Celsius durchgeführt wird.
4. Verfahren gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die dritte Phase der Pyrolyse bei einer Temperatur zwischen 480 und 580 Grad Celsius durchgeführt wird.
5. Verfahren gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die dritte Phase mit der Karbonisation während 20 bis 30 Minuten durchgeführt wird.
6. Verfahren gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Pyrolyse ohne Oxidationsmittel durchgeführt wird.
7. Verfahren gemäß Anspruch 6, dadurch gekennzeichnet, daß die elektromagnetische Bestrahlung mit Wellenimpulsen mit einer Frequenz zwischen 800 und 1100 MHz durchgeführt wird.
8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, daß die elektromagnetische Bestrahlung mit Wellenimpulsen mit einer Frequenz zwischen 900 und 1000 MHz durchgeführt wird.
9. Verfahren gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Verdichtung durch Kompression mit einem Druck von 200 bis 300 kPa durchgeführt wird.
10. Verfahren gemäß einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die biochemische Vorbehandlung ohne Zufuhr von Oxidationsmitteln durchgeführt wird und daß, zwischen der Vorbehandlung und der Pyrolyse, keine Oxidationsmittel gestattet sind.
11. Verfahren gemäß einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß von organischem Material ausgegangen wird, das einen Trockenstoffgehalt von mehr als 50 % aufweist.
12. Ruß, hergestellt gemäß dem Verfahren gemäß einem der vorgenannten Ansprüche.
13. Ruß gemäß Anspruch 12, dadurch gekennzeichnet, daß er eine spezifische Oberfläche aufweist, gemessen durch die C02-Absorption, zwischen 35 und 250 m2/g, eine Jodoberfläche von zumindest 380 m2/g, einen PH-Wert von weniger als 5, einen DBF-Wert von mehr als 200 ml pro 100 g und eine Jodadditionsziffer von mehr als 380 g pro kg.
EP91915755A 1990-09-12 1991-09-11 Verfahren zur herstellung von russ und also hergestelltes russ Expired - Lifetime EP0548130B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
BE9000873 1990-09-12
BE9000873A BE1004586A3 (nl) 1990-09-12 1990-09-12 Werkwijze ter bereiding van roet en aldus bereid roet.
PCT/BE1991/000063 WO1992004414A1 (en) 1990-09-12 1991-09-11 Process for manufacturing carbon black and thus manufactured carbon black

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EP0548130A1 EP0548130A1 (de) 1993-06-30
EP0548130B1 true EP0548130B1 (de) 1994-12-28

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EP91915755A Expired - Lifetime EP0548130B1 (de) 1990-09-12 1991-09-11 Verfahren zur herstellung von russ und also hergestelltes russ

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EP (1) EP0548130B1 (de)
AT (1) ATE116350T1 (de)
BE (1) BE1004586A3 (de)
DE (1) DE69106375D1 (de)
WO (1) WO1992004414A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19955219B4 (de) * 1998-11-21 2008-08-28 Heidrich, Jens, Dipl.-Ing. Verfahren und Vorrichtung zur Desintegration von Biomassen

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2009305468A1 (en) 2008-10-16 2010-04-22 Evonik Carbon Black Gmbh Carbon black, method for the production thereof, and use thereof
US9916914B2 (en) 2011-09-07 2018-03-13 The Governors Of The University Of Alberta N-doped carbon materials
JP2022512970A (ja) * 2018-11-07 2022-02-07 リビング・インク・テクノロジーズ，エルエルシー 生物学的インク及びコーティング、並びに関連する方法
US11739219B2 (en) 2020-05-07 2023-08-29 Living Ink Technologies, Llc Biologically-derived carbon black alternative and method of making the same
US20230407042A1 (en) * 2020-10-30 2023-12-21 Orion Engineered Carbons Gmbh Rubber Compositions Comprising Carbon Black Obtained From Renewable Feedstock
KR20220060042A (ko) * 2020-11-02 2022-05-11 재단법인 한국탄소산업진흥원 온도구배가 가능한 반응로를 이용한 아세틸렌 블랙 제조장치

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3843457A (en) * 1971-10-14 1974-10-22 Occidental Petroleum Corp Microwave pyrolysis of wastes
US4219415A (en) * 1978-08-09 1980-08-26 Nassef N A Method and apparatus for disposal of organic wastes
FR2484294B1 (fr) * 1980-06-17 1985-06-28 Lejeune Gwenole Procede et dispositif de traitement de produits humides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19955219B4 (de) * 1998-11-21 2008-08-28 Heidrich, Jens, Dipl.-Ing. Verfahren und Vorrichtung zur Desintegration von Biomassen

Also Published As

Publication number Publication date
EP0548130A1 (de) 1993-06-30
ATE116350T1 (de) 1995-01-15
BE1004586A3 (nl) 1992-12-15
WO1992004414A1 (en) 1992-03-19
DE69106375D1 (de) 1995-02-09

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